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1.
Chem Commun (Camb) ; 2020 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-33236739

RESUMO

The two isomers of the propylperoxy radical 1-C3H7O2 and 2-C3H7O2, together with their individual rotamers, are identified and assigned by threshold photoelectron spectroscopy with the aid of high-level theoretical computations, from which their accurate adiabatic ionization energies are derived. This study paves the way to probing elusive peroxy radicals and their isomers in advanced mass spectrometry analysis of combustion and atmospheric reactions.

2.
J Chem Phys ; 153(12): 124306, 2020 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-33003730

RESUMO

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO2), a key reaction intermediate in combustion and atmospheric chemistry as well as astrochemistry, using double imaging photoelectron photoion coincidence spectroscopy. The HO2 radical is formed in a microwave discharge flow tube reactor through a set of reactions initiated by F atoms in a CH4/O2/He gas mixture. The high-resolution threshold photoelectron spectrum of HO2 in the 11 eV-12 eV energy range is acquired without interferences from other species and assigned with the aid of theoretically calculated adiabatic ionization energies (AIEs) and Franck-Condon factors. The three vibrational modes of the radical cation HO2 +, the H-O stretch, the H-O-O bend, and the O-O stretch, have been identified, and their individual frequencies are measured. In addition, the AIEs of the X3A″ ground state and the a1A' first excited electronic state of HO2 + are experimentally determined at 11.359 ± 0.003 eV and 11.639 ± 0.005 eV, respectively, in agreement with high-level theoretically computed results. Furthermore, the former AIE value provides validation of thermochemical networks used to extract the enthalpy of formation of the HO2 radical.

3.
J Chem Phys ; 153(13): 134303, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-33032417

RESUMO

Using a synchrotron-based Fourier-transform spectrometer, the high-resolution absorption spectra of the C1-symmetric 2,3-dihydrofuran (23DHF) and C2v-symmetric 2,5-dihydrofuran (25DHF) have been measured from 5.5 eV to 9.4 eV with an absolute absorption cross section scale. Oscillator strengths and vertical excitation energies of the lowest 18 states have been computed using the average of the second- and third-order algebraic diagrammatic construction polarization propagator method and the equation-of-motion coupled-cluster method at the level of singles and doubles model. These show that the bright valence transitions of ππ*-character are embedded into Rydberg transitions, whose oscillator strengths are at least one order of magnitude lower. To account for intensity borrowing, the first broad valence transition between 5.5 eV and 6.8 eV was simulated using a nuclear ensemble, and the agreement between experiment and theory is excellent. Whereas 23DHF only exhibits one broad valence transition followed by d/f Rydberg series converging to the ionization energy, the absorption spectrum of 25DHF has four bands, attributed to a valence nπσ → π*-transition, nπσ → 3px,z/3dxz transitions, a second valence nπ → π*-transition followed by d/f Rydberg series converging to the ionization energy, respectively. All Rydberg series converging to the ionization energy have been characterized in terms of their quantum defects.

4.
Phys Chem Chem Phys ; 22(37): 21068-21073, 2020 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-32939522

RESUMO

We report a comprehensive vacuum ultraviolet (VUV) photoionization study of the nitrogen dioxide dimer (NO2)2 by using a state-of-the-art method of double imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy at synchrotron SOLEIL. We find that the dimer cation N2O4+ from direct ionization of (NO2)2 is not stable and fully dissociates into the NO2+ and NO2 fragments. After identifying and separating the two different sources of NO2+ cations observed in experiments, direct photoionization of the monomer NO2 and dissociative photoionization of the co-existing dimer (NO2)2, the pure mass-selected threshold photoelectron spectrum (TPES) of the dimer (NO2)2 has been recorded without the need of subtraction. An upper limit of the adiabatic ionization energy of the dimer (AIE ≤ 9.59 ± 0.05 eV) and the appearance energy of the NO2+ fragment (AE = 10.15 ± 0.05 eV) are also given. In addition, the state-selected dynamics of the five low-lying electronic states of the cation N2O4+ have been analyzed from the corresponding kinetic energy release distributions.

5.
J Chem Phys ; 153(3): 034302, 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32716160

RESUMO

A fresh perspective on the interaction of electron and nuclear motions in photon induced dynamical processes can be provided by the coupling of photoelectron angular distributions and cation vibrational states in the photoionization of chiral molecules using circularly polarized radiation. The chiral contributions, manifesting as a forward-backward asymmetry in the photoemission, can be assessed using Photoelectron Circular Dichroism (PECD), which has revealed an enhanced vibrational influence exerted on the outgoing photoelectron. In this paper, we investigate the PECD of a rigid chiral monoterpene, 3-carene, using single-photon vacuum ultraviolet ionization by polarized synchrotron radiation and selecting energies from the ionization threshold up to 19.0 eV. By judicious choice of these photon energies, two factors that influence PECD asymmetry values, electron kinetic energy and ion vibrational level, can be effectively isolated, allowing a clear demonstration of the very marked vibrational effects. A slow photoelectron spectrum is used to examine the vibrational structure of the isolated outermost valence (HOMO) photoelectron band, and peak assignments are made with the aid of a Franck-Condon simulation. Together, these provide an estimate of the adiabatic ionization energy as 8.385 eV. The reported chiral asymmetry from the randomly oriented 3-carene enantiomers reaches a maximum of over 21%. Theoretical PECD calculations, made both for the fixed equilibrium molecular geometry and also modeling selected normal mode vibration effects, are presented to provide further insight.

6.
J Chem Phys ; 153(3): 031101, 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32716172

RESUMO

We present here a synchrotron radiation vacuum ultraviolet photoionization study of the simplest alkoxy radical, CH3O, a key reaction intermediate in atmospheric and combustion chemistry. A microwave discharge fast flow tube connected to a molecular beam sampling system is employed as a chemical reactor to initiate reactions and generate radicals. The CH3O+ cation from direct ionization of the CH3O radical is detected successfully in the photoionization mass spectrum close to its ionization threshold. In addition, after identifying and removing the contribution of the 13C-isotopic formaldehyde H2 13CO with the same isobaric mass m/z = 31, the high-resolution threshold photoelectron spectrum of CH3O is obtained and assigned with the aid of calculated Franck-Condon factors. The adiabatic ionization energy of CH3O is determined at 10.701 eV with an accuracy of 0.005 eV.

7.
Phys Chem Chem Phys ; 22(25): 13880-13892, 2020 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-32396927

RESUMO

We present the photoionization dynamics of the C60 buckminsterfullerene from threshold up to 14.0 eV recorded with VUV synchrotron radiation at the DESIRS beamline at the SOLEIL synchrotron. The recorded data is obtained using a double-imaging photoelectron photoion coincidence spectrometer and is presented as a two-dimensional photoelectron matrix which contains a wealth of spectroscopic data. We present these data in an astrophysical context which relates to (i) the threshold photoelectron spectrum which is compared to data relevant to the diffuse interstellar bands (DIBs), (ii) the kinetic photoelectron distribution at the Lyman-α line which is relevant to the dominant heating source in the ISM, and (iii) the absolute photoionization cross section of C60 up to approx. 10.5 eV. The photoelectron spectrum implies that the symmetry of the ground state is different than previous theoretical models have predicted, and this result is discussed in context of recent experimental and theoretical findings. Also presented are partial photoionization cross sections of the first two photoelectron bands and their anisotropy parameters. These data are compared with previous theoretical values and discussed where appropriate.

8.
Phys Chem Chem Phys ; 22(23): 12886-12893, 2020 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-32315003

RESUMO

The valence-shell photoionization of formaldehyde is investigated by means of combining Photo-Electron Photo-Ion COincidence (PEPICO) experiments and ab initio calculations. The formation of three ion fragments: HCO+, CO+ and H, via dissociative photoionization following excitation at 17 eV is discussed. The experimental results consisting of electron-ion kinetic energy correlation diagrams for the corresponding coincident events, i.e. (HCO+, e-), (CO+, e-) and (H, e-), as well as the fragment abundance as a function of the binding energy, are complemented by high level electronic structure calculations including potential energy curves and on-the-fly trajectories. The results are consistent with a main relaxation process via internal conversion into rovibrationally excited levels of the H2CO+ ground state, followed by statistical dissociation, preferentially into HCO+. The analysis of the experimental results reveals nevertheless the signature of a conical intersection controlling the dynamics and favoring dissociation into the molecular channel, CO+ + H2. In addition, the minor formation of the H ion is suggested to occur through a roaming pathway on the cation excited state.

9.
J Chem Phys ; 152(10): 104301, 2020 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-32171217

RESUMO

The vacuum ultraviolet photoionization of the methyl peroxy radical, CH3O2, and unimolecular dissociation of internal energy selected CH3O2 + cations were investigated in the 9.7-12.0 eV energy range by synchrotron-based double imaging photoelectron photoion coincidence. A microwave discharge flow tube was employed to produce CH3O2 via the reaction of methyl radicals (CH3) with oxygen gas. After identifying and separating the different sources of CH3 + from photoionization of CH3 or dissociative photoionization of CH3O2, the high resolution slow photoelectron spectrum (SPES) of CH3O2 was obtained, exhibiting two broad bands superimposed with a complex vibrational structure. The first band of the SPES is attributed to the X3A″ and a1A' overlapped electronic states of CH3O2 + and the second is assigned to the b1A' electronic state with the help of theoretical calculations. The adiabatic ionization energy of CH3O2 is derived as 10.215 ± 0.015 eV, in good agreement with high-accuracy theoretical data from the literature. The vertical ionization energy of the b1A' electronic state is measured to be 11.5 eV and this state fully dissociates into CH3 + and O2 fragments. The 0 K adiabatic appearance energy (AE0K) of the CH3 + fragment ion is determined to be 11.15 ± 0.02 eV.

10.
Phys Chem Chem Phys ; 22(4): 1974-1982, 2020 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-31932822

RESUMO

Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of NO2 in the 10.0-15.5 eV energy range have been investigated in detail by using high-resolution double imaging photoelectron photoion coincidence (i2PEPICO) at synchrotron SOLEIL. Five low-lying electronic states of the NO2+ cation, X1Σg+, a3B2, b3A2, A1A2 and B1B2, are prepared with well-resolved vibronic structures and their state-specific dissociation mechanisms are unraveled and discussed. The present experimental results clarify that except the X1Σg+ ground electronic state and the first three vibrational levels of the a3B2 electronic state, the other cationic states of NO2+ within the present energy range are totally dissociative towards the NO+(X1Σ+) + O(3P) and/or NO+(X1Σ+) + O(1D) dissociation limits. An energy barrier exists along the direct dissociation route of the a3B2 state, and the b3A2 electronic state is a quasi-bound state with a very shallow well, both of which adiabatically correlate to the NO+(X1Σ+) + O(3P) dissociation limit. The a3B2 state mainly with bending vibration excitations undergoes a non-adiabatic transition to the 23A''(3B1) repulsive state along its bending potential energy curve and then predissociates into the NO+(X1Σ+) + O(3P) products. Our experimental results firstly demonstrate that the NO+(X1Σ+, v) fragment ions produced from individual vibronic levels of the dissociative NO2+(a3B2, b3A2) states are produced at the v = 0 ground vibrational level with a high rotational population due to the excitation of the vibrational bending mode of NO2+ and the associated imparted torque upon dissociation. The slower predissociations of the A1A2 and B1B2 electronic states via their spin-orbit couplings with the repulsive 23A''(3B1) state produce the NO+(X1Σ+) and O(3P) fragments with a long vibrational progression. In addition, the B1B2 state can also undergo a radiationless transition such as internal conversion into the hot X1Σg+ state and then dissociate into the second dissociation channel correlated to the NO+(X1Σ+) and O(1D) products.

11.
Phys Chem Chem Phys ; 22(3): 1222-1241, 2020 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-31850421

RESUMO

Through the use of tunable vacuum ultraviolet light generated by the DESIRS VUV synchrotron beamline, a jet-stirred reactor was coupled for the first time to an advanced photoionization mass spectrometer based upon a double imaging PhotoElectron PhotoIon COincidence (i2PEPICO) scheme. This new coupling was used to investigate the low-temperature oxidation of n-pentane, a prototype molecule for gasoline or diesel fuels. Experiments were performed under quasi-atmospheric pressure (1.1 bar) with a residence time of 3 s for two equivalence ratios (1/3 and 0.5) with a fuel initial mole fraction of 0.01. The measured time-of-flight mass spectra are in good agreement with those previously obtained with other photoionization mass spectrometers and, like those previous ones, display several m/z peaks for which the related species assignation is ambiguous. This paper shows how the analysis of the coincident mass-tagged Threshold PhotoElectron Spectra (TPES) together with first principle computations, consisting of the determination of the adiabatic ionization energies and the spectra of some products, may assist products' identification. The results mostly confirm those previously obtained by photoionization mass spectrometry and gas chromatography, but also allow a more accurate estimation of the 1-pentene/2-pentene mole fraction ratio. Our data also indicate a higher formation of acetone and methyl ethyl ketone than what is predicted by current models, as well as the presence of products that were not previously taken into account, such as methoxyacetylene, methyl vinyl ketone or furanone. The formation of three, four and five membered ring cyclic ethers is confirmed along with linear ketones: 2- and 3-pentanone. A significant general trend in indicating higher amounts of ketones than are indicated by gas chromatography is noted. Finally, TPES of alkenylhydroperoxides are also provided for the first time and constrains on the isomers identification are provided.

12.
Phys Chem Chem Phys ; 21(46): 25907-25915, 2019 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-31742264

RESUMO

We present the absolute photoionization cross-section of the mercapto radical, SH, recorded from its first ionization energy at 10.4 eV up to a photon energy of 15 eV. The absolute scale was calibrated at the fixed photon energy of 11.2 eV using the known values of H2S and S as references. SH and S were produced in a microwave discharge flow-tube reactor by hydrogen abstraction of the H2S precursor. The measured photoionization cross-section of SH dramatically differs from the one currently employed to model the presence of this species in a number of astronomical environments, where SH along with its ionic counterpart SH+ have been detected. The cation spectroscopy and fragmentation of H2S, SH and S in the 9.2-15.0 eV energy range obtained using threshold photoelectron techniques is also presented and discussed in the context of existing literature.

13.
J Phys Chem A ; 123(42): 9193-9198, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31556614

RESUMO

We report on the photoionization of the resonance-stabilized anilino radical (C6H5NH) formed by H atom abstraction from aniline by F atoms in a flow tube. The spectra were recorded from 7.8 to 9.7 eV by using a double-imaging photoelectron/photoion coincidence spectrometer with VUV radiation provided by the DESIRS beamline at the SOLEIL synchrotron. The vibrationally resolved recorded threshold photoelectron spectrum of the anilino radical showed transitions to the ground X+1A' ← X2A″ and first excited states a+3A″ ← X2A″ of the cation, which were assigned through comparison with theoretically simulated spectra, yielding an adiabatic ionization energy of 8.02 ± 0.02 eV. These results are discussed in light of existing data on the picolyl structural isomers and are of interest for the analytical applications of coincidence techniques in real-time combustion analysis where these intermediates are found.

14.
J Phys Chem A ; 123(16): 3551-3557, 2019 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-30943036

RESUMO

Action spectroscopy using photon excitation in the VUV range (photon energy 4.5-9 eV) was performed on protonated uracil (UraH+) and uridine (UrdH+). The precursor ions with m/ z 113 and m/ z 245, respectively, were produced by an electrospray ionization source and accumulated inside a quadrupole ion trap mass spectrometer. After irradiation with tunable synchrotron radiation, product ion mass spectra were obtained. Fragment yields as a function of excitation energy show several maxima that can be attributed to the photoexcitation into different electronic states. For uracil, vertically excited states were calculated using the equation-of-motion coupled cluster approach and compared to the observed maxima. This allows to establish correlations between electronic states and the resulting fragment masses and can thus help to disentangle the complex de-excitation and fragmentation pathways of nucleic acid building blocks. Photofragmentation of the nucleoside uridine shows a significantly lower variety of fragments, indicating stabilization of the nucleobase by the attached sugar.

15.
Front Chem ; 7: 222, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31032247

RESUMO

Photoelectron/photoion imaging spectrometry employing dispersed VUV radiation from the SOLEIL synchrotron has been used to study the predissociation of N2 + states located up to 1.3 eV above the ion's first dissociation limit. Branching ratios for unimolecular decay into either N2 + or N+ were obtained by measuring coincidences between threshold electrons and mass-selected product ions, using a supersonic beam of either 14N2 or 15N2 as photoionization target. The results confirm that predissociation of the C 2 Σ u + state of 14N2 + is faster than emission to the electronic ground-state by a factor 10 or more for all vibrational levels v' ≥ 3, while for 15N2 + the two decay modes have comparable probabilities for the levels v' = 3, 4, and 5. In contrast, no significant isotope effect could be observed for the other states of N2 + identified in the photoelectron spectrum. For both 14N2 + and 15N2 + isotopologues all vibrational levels of these other states decay to an extent of at least 95% by predissociation.

16.
Phys Chem Chem Phys ; 20(37): 24263-24286, 2018 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-30211409

RESUMO

Atmospheric pressure plasmas are sources of biologically active oxygen and nitrogen species, which makes them potentially suitable for the use as biomedical devices. Here, experiments and simulations are combined to investigate the formation of the key reactive oxygen species, atomic oxygen (O) and hydroxyl radicals (OH), in a radio-frequency driven atmospheric pressure plasma jet operated in humidified helium. Vacuum ultra-violet high-resolution Fourier-transform absorption spectroscopy and ultra-violet broad-band absorption spectroscopy are used to measure absolute densities of O and OH. These densities increase with increasing H2O content in the feed gas, and approach saturation values at higher admixtures on the order of 3 × 1014 cm-3 for OH and 3 × 1013 cm-3 for O. Experimental results are used to benchmark densities obtained from zero-dimensional plasma chemical kinetics simulations, which reveal the dominant formation pathways. At low humidity content, O is formed from OH+ by proton transfer to H2O, which also initiates the formation of large cluster ions. At higher humidity content, O is created by reactions between OH radicals, and lost by recombination with OH. OH is produced mainly from H2O+ by proton transfer to H2O and by electron impact dissociation of H2O. It is lost by reactions with other OH molecules to form either H2O + O or H2O2. Formation pathways change as a function of humidity content and position in the plasma channel. The understanding of the chemical kinetics of O and OH gained in this work will help in the development of plasma tailoring strategies to optimise their densities in applications.

17.
Phys Chem Chem Phys ; 20(32): 20756-20765, 2018 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-29989120

RESUMO

Adenine, a DNA base, exists as several tautomers and isomers that are closely lying in energy and that may form a mixture upon vaporization of solid adenine. Indeed, it is challenging to bring adenine into the gas phase, especially as a unique tautomer. The experimental conditions were tuned to prepare a jet-cooled canonical adenine (9H-adenine). This isolated DNA base was ionized by single VUV photons from a synchrotron beamline and the corresponding slow photoelectron spectrum was compared to ab initio computations of the neutral and ionic species. We report the vibronic structure of the X+ 2A'' (D0), A+ 2A' (D1) and B+ 2A'' (D2) electronic states of the 9H adenine cation, from the adiabatic ionization energy (AIE) up to AIE + 1.8 eV. Accurate AIEs are derived for the 9H-adenine (X[combining tilde] 1A') + hν → 9H-adenine+ (X+ 2A'', A+ 2A', B+ 2A'') + e- transitions. Close to the AIE, we fully assign the rich vibronic structure solely to the 9H-adenine (X 1A') + hν → 9H-adenine+ (X+ 2A'') transition. Importantly, we show that the lowest cationic electronic states of canonical adenine are coupled vibronically. The present findings are important for understanding the effects of ionizing radiation and the charge distribution on this elementary building block of life, at ultrafast, short, and long timescales.


Assuntos
Adenina/química , Cátions , Isomerismo , Cinética , Modelos Moleculares , Estrutura Molecular , Transição de Fase , Processos Fotoquímicos , Fenômenos Físicos , Teoria Quântica , Termodinâmica
18.
J Phys Chem Lett ; 9(13): 3604-3611, 2018 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-29902010

RESUMO

We report an investigation of lead halide perovskite CH3NH3PbBr3 nanocrystals and associated ligand molecules by combining several different state-of-the-art experimental techniques, including synchrotron radiation-based XPS and VUV PES of free-standing nanocrystals isolated in vacuum. By using this novel approach for perovskite materials, we could directly obtain complete band alignment to vacuum of both CH3NH3PbBr3 nanocrystals and the ligands widely used in their preparation. We discuss the possible influence of the ligand molecules to apparent perovskite properties, and we compare the electronic properties of nanocrystals to those of bulk material. The experimental results were supported by DFT calculations.

19.
J Am Soc Mass Spectrom ; 29(9): 1826-1834, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-29949057

RESUMO

The nonapeptide oxytocin (OT) is used as a model sulfur-containing peptide to study the damage induced by vacuum UV (VUV) radiations. In particular, the effect of the presence (or absence in reduced OT) of oxytocin's internal disulfide bridge is evaluated in terms of photo-fragmentation yield and nature of the photo-fragments. Intact, as well as reduced, OT is studied as dianions and radical anions. Radical anions are prepared and photo-fragmented in two-color experiments (UV + VUV) in a linear ion trap. VUV photo-fragmentation patterns are analyzed and compared, and radical-induced mechanisms are proposed. The effect of VUV is principally to ionize but secondary fragmentation is also observed. This secondary fragmentation seems to be considerably enabled by the initial position of the radical on the molecule. In particular, the possibility to form a radical on free cysteines seems to increase the susceptibility to VUV fragmentation. Interestingly, disulfide bridges, which are fundamental for protein structure, could also be responsible for an increased resistance to ionizing radiations. Graphical Abstract.


Assuntos
Ânions/química , Dissulfetos/química , Ocitocina/química , Espectrometria de Massas , Oxirredução , Fotólise , Raios Ultravioleta , Vácuo
20.
J Chem Phys ; 148(12): 124309, 2018 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-29604849

RESUMO

The double imaging photoelectron photoion coincidence technique has been applied to investigate the dissociation of state-selected O2+(32Πu, c4Σu-) ions at hv = 25.4 eV. It is shown that the O2+ ions prepared in the 32Πu inner-valence state can dissociate toward two channels where a distinct changeover from the third dissociation limit O(3P) + O+(2D) to the fifth limit O(3P) + O+(2P) is observed at a binding energy of ∼23.8 eV. Up to four dissociation limits have been identified in the dissociation of the v = 0 vibrational level of the c4Σu- electronic state, and in particular, the products toward the third limit with a very weak intensity are definitely identified and assigned. In addition, the individual contributions of the two superimposed 32Πu and c4Σu- states to the fifth dissociation limit are clearly separated and determined for the first time. The anisotropy parameters of the O+ fragment ion toward different dissociation limits have also been measured and exhibit specific state-selected characteristics. The dissociation mechanisms of the 32Πu and c4Σu- states including predissociation and tunneling motion are proposed based on the present experimental results and the existing theoretical potential energy curves.

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